Trisazo dyestuffs and process of producing them



Patented Mar. 4, 1930 I UNITED STATES PATENT oFFieE S'IGNOR TO GENERAL ANILIN E WORKS, OF DELAWARE TRISAZO DYESTUFFS AND P INC., OF NEW YORK, N. Y., A CORPORATION ROCESS OF PROPUCING THEM No Drawing. Application filed February 4, 1927, Serial No. 166,009, and in Germany February 26, 1926.

In United States Patent No. 1,602,991 there have been described processes for the manufacture of tri'sa'zo dyestuffs comprising coupling the diazo compounds of secondary disazo dyestuffs, containing in the end position 1-amino-2-naphthol-ethyl-ether-G-sulphonic acid. with 2-amino-5-naphthol-7-sulphonic-acid or 2-aryl amino-5snaphthol-7- sulphonic acid, in the presence of pyridine or a derivative or homologue thereof.

The said secondary disazo dyestufi's may be represented broadly by the general formula wherein R and R represent residues of th benzene or naphthalene series or their sulfonic acids, and X represents alkyl.

- 7-sulphonic acid. other derivatives of the 2-amino-5-naphthol-7-sulphonic acid. Thus,

for example, 2-alkvl-amino-5-naphthol-7- sulphonic acids, 2-aralkvlamino-5-naphthol- 7-sulphonic acids, 2'-aroyl-amino-5-naphthol-7-sulphonic acids or their substitution products may be employed and, further, 5.5 dihydroxv 7.7 disulfo 2.2 dinaphthyl-urea, having most probably the formula:

H038 soar! 1.2 -naphthimidazol 5 hydroxy 7-sulphonic acids having most probably the formula:

o -x nso; N

wherein X represents hydrogen or -NH one X being hydrogen. and one X being NH mand p-amino-phenyl-l.Q-naphl thothiazol-5-hydroxy-7-sulphonic-acids having most probably the formula:

wherein X represents hydrogen or NH one X being hydrogen, and one X being 'NH and the like.

The above-mentioned derivatives of 2- amino-fi-naphthol-7-sulphonic acid may be represented broadly by the general formula:

wherein Z represents hydrogen or the second heterocyclic atom in one of the grouping thiazole or diazole in which the nitrogen atom in the 2-position is the first heterocyclic atom, and in which Y represents one of the residues, alkyl, aralkyl, aroyl, aminoaryl or the carbon atom of the thiazole or diazole ring.-

The following examples illustrate the invention:

Ewample 1 SOIH is soluble in water, readily soluble in concentrated sulfuric acid with a blue colora- CH: HaSON=N N=N tidn, and yields, upon carefill reduction with stannous chloride and hydrochloric acid:

Aniline-3.6-disulphonic acid, l--naphthylenediamine, 1-4-diamino-Q-naphthol-ethyl ether-G-sulphonic acid, and 2 ethyl amino 5 --hydroxy- 6 naplithy'lamin'e-7-sulphonic acid.

It dyes cotton in clear greenish blueshades of good fastness properties.

By replacing thev 2-ethyl-amino-5-naphthol-7-sulphonic acidof the foregoing ex-' ample by Q-dieth l-amino-5-naphthol-7-sulphonic acid or y 5.5-dihydroxy-2.2di naphthylamine-7.Z'-disulphonic acid or by the carbonyl-2-amino-5-naPhtholJZ-sulphon-' ic acid or by the mixed urea from Q-amino- The finished dyestufi, having most proba- 5-naphthol-7-s1ilphonic acid and ammonia .or a substituted or unsubstituted arylamine,

dyestuffs are obtained possessing similar properties.

Example '2 86.8 parts by weight of the sodium salt of the dyestufi' o-toluidine-disulphonic acidazo- 1 -naphthyl-amino- 7 -sulphonic-acid-azo- Q 1- amino-Q-naphtholethylether- 6 -sulphonic acid are diazotized and coupled with 35.5 parts by weight of m-amino-phenyl-L2- naphthimidazol-5-hydroxy-7-sulphonic acid in an ice cold solution of 50.parts of water and 100 parts by weight of pyridine. When the coupling is complete the dyestufi 'is worked up in the customary manner.

bly the formula:

dissolves in concentrated sulfuric acid with a cornfiower blue coloration, and upon careful reduction with stannous chloride and hydrochloric acid, yields:

o-toluidine-disulfonic acid, 1.4-naphthalenediamine-7-sulfo acid, lA-diamino-Q-naphthol ethyl-ether-G-sulfonic-acid, and A In-amino-phenyl -l.2-naphthimidazol-6.5-

aminonaphthol-7-sulfonic-acid.

It dyes cotton blueish green shades.

The above dyestufi' can be dia'zotized on the fiber and developed with methylphenyl py- 1 razolone, when a fast green shade results. The latter dyestuif, developed upon the fiber, most probably has the formula;

Ewample 3 75.1 parts by Weight of the sodium salt of the dyestufl. o-sulphanilic-acid-azo-l-naphthylamine-7-sulphonic 4 acid-azo 1-amin0-2- naphthol-ethyl-ether-6-sulphonic-acid are diazotized and coupled with 35.8 parts by weight of m-aminobenzoyl-2-amino-5-naph- .thol-7-sulphonic-acid in the presence of 50 noas Dyestuffs having similar properties to those of the dyestufi of the foregoing example are obtainable by replacing the m-aminobenzoyl-Q-amino- 5 naphthol 7 sulphonicacid by the p-aminobenzoyl-2 amino-5-naphthol-7-sulphonic-acid or by mor p-aminophenyl 5 hydroxy 1.2 naphthothiazol 7- sulphnoic-acids or by the mor p-amin'o-benzoyl aminobenzoyl- 5 -naphthol- 7 -sulphonicacids.

I claim: 1 I

1. Process for' the production of .trisaz'o' dyestuffs involving the coupling, in the presence of pyridine, of the diazo compound of a secondary disazo dyestuff containing 1 amino 2 naphthol ethyl ether fi-sulfonic acid in' the end position with a derivative of 2-amino-5-naphthol-7-sulfonic acid, characterized inthat the said derivative of Q-amino-5-naphthol-7-sulfonic acid is a compound having the general formula:

ence of pyridine, of the diazo compound of a secondary disazo dyestulf having the general wherein R and R represent residues of the benzene or naphthalene series respectively or their sulfoni c acids and X represents alkyl, with a derivative of 2-amino-5-naphthol-7- sulfonic acid, characterized in that the said derivative of 2-amino-5-naphthol-7-sulfonic acid is a compound having the general formula:

heterocyclic atom in one of the grouping thiazole or diazole in which the nitrogen atom in the 2-position is the first heterocyclic atom, and in which Y represents one of the residues, alkyl, aralkyl, aroyl, aminoaryl or the carbon atom of the thiazole or diazole ring.

3. The herein described new trisazo dyestufi's having most probably .the general formula wherein R and R represent residues of the benzene or naphthalene series respectively or their sulfonic acids, X represents alkyl, Z

represents hydrogen or the second heterocyclic atom in one of the -grouping thiazole or diazole in which the nitrogen atom in the 2-p'osition is the first heterocyclic atom, and in which Y represents one of the residues, alkyl, aralkyl, aroyl, aminoaryl or the carbon atom of the thiazole or diazole ring which dyestuffs are soluble in concentrated sulfuric acid generally with from blue to bluish green colorations; dyeing cotton generally from blue to green shades.

4. The herein described new trisazo dyestuffs having most probably the general formula:

Z Y B N=NR'-N=N .CaHs H wherein R and R represent residues of the benzene or naphthalene series respectively or their sulfonic acids, Z represents hydrogen or the second heterocyclic atom in one 01: the grouping thiazole or dia-zole in which the nitrogen atom. in the 2-position is the first heterocyclic atom, and in which Y represents one of the'residues, alkyl, aralkyl, aroyl,

aminoaryl or the carbon atom of the thiazole or diazole ring, which dyestuffs are soluble Cal in concentrated sulfuric acid generally with from blue to bluish green colorations; dyeing cotton generally from blue to green shades.

v 5.'The herein described new trisazo dye-, stuff having most probably the general formula which dyestufi is readily soluble in concentrated sulfuric-acid with a blue coloration, yielding upon careful reduction with stannous chloride and hydrochloric acid aniline 3.6-disulfohic-acid, l-l-naphthylenediamine, 1- 4 diamino -2- naphtholethyl ether 6 sulfonic acid, and 2-ethylamino-5-hydroxy-6- naphthylamine-7-sulfonic-acid; dyeing c0tton clear greenish blue shades of good fast- 5 ness properties.

In testimony whereof, I aflix my signature.

HUGO SCHWEITZER. 

